CN110286115A - A kind of SERS substrate and preparation method based on paper fiber substrate - Google Patents
A kind of SERS substrate and preparation method based on paper fiber substrate Download PDFInfo
- Publication number
- CN110286115A CN110286115A CN201910606295.XA CN201910606295A CN110286115A CN 110286115 A CN110286115 A CN 110286115A CN 201910606295 A CN201910606295 A CN 201910606295A CN 110286115 A CN110286115 A CN 110286115A
- Authority
- CN
- China
- Prior art keywords
- gold nano
- nano grain
- paper fiber
- substrate
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 95
- 239000000835 fiber Substances 0.000 title claims abstract description 60
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000010931 gold Substances 0.000 claims abstract description 69
- 229910052737 gold Inorganic materials 0.000 claims abstract description 69
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000001514 detection method Methods 0.000 claims abstract description 26
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims abstract description 14
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 239000000084 colloidal system Substances 0.000 claims abstract description 3
- 239000000123 paper Substances 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001548 drop coating Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000005031 sulfite paper Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- DRGATGNRWLXDLH-UHFFFAOYSA-M gold;tetraoctylazanium;bromide Chemical compound [Br-].[Au].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC DRGATGNRWLXDLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 claims description 2
- 239000002362 mulch Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 claims description 2
- DTNJZLDXJJGKCM-UHFFFAOYSA-K sodium;trichlorogold Chemical compound [Na].Cl[Au](Cl)Cl DTNJZLDXJJGKCM-UHFFFAOYSA-K 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 5
- 238000001311 chemical methods and process Methods 0.000 abstract description 2
- 238000005253 cladding Methods 0.000 abstract 1
- 235000013339 cereals Nutrition 0.000 description 42
- 238000001069 Raman spectroscopy Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 239000002082 metal nanoparticle Substances 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 230000002708 enhancing effect Effects 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical class CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
A kind of SERS substrate and preparation method based on paper fiber substrate, belongs to phasmon nanophotonics and optical sensing technology field.It is stained with the gold nano grain of surface cladding ammonium bromide and tetraoctyl ammonium bromide on paper fiber substrate surface, forms detection zone, the partial size of gold nano grain is 100-160nm；There is between gold nano grain gap in detection zone.The gold nano-particle colloid and low temperature heat treatment of ammonium bromide and tetraoctyl ammonium bromide are coated with based on the surface that common paper fiber and conventional chemical processes synthesize.And its photophysics characteristic, SERS performance and detection sensitivity can achieve the level of current high-end technology of preparing.
Description
Technical field
The invention belongs to phasmon nanophotonics and optical sensing technology field.It is proposed a kind of easy, easy paper
Fiber over-assemble metal nanoparticle realizes SERS substrate, the trace detection for substance.
Background technique
Raman scattering is inelastic scattering, and Raman diffused light is unrelated with incident light frequency relative to the frequency displacement of incident light, and
Correspond to the vibration and rotation information of characterization of molecules.Therefore, Raman spectrum can disclose the structure of substance, can be to substance
Identify and content is identified.But since scattered light intensity is weaker, the identification and detection of microscratch quantity of material face very big challenge.
SERS has very high sensitivity, and advantage is the Electromagnetic enhancement that it has and Chemical enhancement performance, be it is a kind of very
Good surface optical sensing technology.SERS, which is detected, is based primarily upon metal Nano structure phasmon Localized field enhancement effect, and this
Kind enhancement effect depends on the size of metal Nano structure, gap, the i.e. density and intensity of SERS hot spot.In " hot spot "
The Raman scattering intensities of punishment can be greatly enhanced.The plasmon resonance spectrum of the nanostructures such as gold, silver, copper covers
Entire visible light and near infrared band, are widely used in the preparation of SERS substrate.Pass through optimization metal using all kinds of methods
The available biggish enhancement factor of the structure of base material, such as prepare using chemical synthesis the metal of different scale topographies
Nano particle.The technologies such as vapor phase deposition, offset printing, etching, nanoparticle assembling are additionally based in substrates such as quartz plate, silicon wafers
Upper SERS substrate obtained, has also embodied excellent performance in trace materials detection.Prepare the two dimension in planar substrates
The SERS enhancement effect of metal Nano structure is limited relative to three-dimensional structure phasmon and SERS enhancement effect, and exists
Planarization, templating, the problems such as uneven, preparation process is complicated.
It, can be with shape using the space three-dimensional distribution character that paper fiber provides in paper fiber substrate over-assemble metal nanoparticle
At the SERS " hot spot " of distributed in three dimensions.The space three-dimensional stereochemical structure of paper fiber can not only provide big surface area for adsorbing
More metal nanoparticles, and gold nano grain and its SERS of generation " hot spot " is made to be distributed in three-dimensional to a greater degree
Space, to provide more SERS enhancing hot spots.To significantly improve the testing molecule in space three-dimensional stereochemical structure
Raman signal realizes the detection of identification and the sensitivity of microscratch quantity of material.
Summary of the invention
The present invention provides a kind of SERS substrates and preparation method for trace amounts of substances detection.Its advantageous feature is to make
Preparation Method is simple and low in cost, and the surface synthesized based on common paper fiber and conventional chemical processes is coated with four n-octyl bromides
Change the gold nano-particle colloid and low temperature heat treatment of ammonium.And its photophysics characteristic, SERS performance and detection sensitivity
It can achieve the level of current high-end technology of preparing.
In order to realize that said effect, the present invention are achieved by the steps of:
A kind of SERS substrate based on paper fiber substrate, which is characterized in that be stained with surface on paper fiber substrate surface
The gold nano grain of ammonium bromide and tetraoctyl ammonium bromide is coated, detection zone is formed, the partial size of gold nano grain is 100-160nm；It is detecting
There is between gold nano grain gap in region.
There are multiple detection zones on a paper fiber substrate surface, multiple detection zones form array structure；Detection zone
The size in domain, which can according to need, to be prepared.
In further preferred each detection zone, the superficial density in gold nano grain mulch paper fibrous substrate region are as follows: gold
It does not include 0 and 100%, preferably 10%- that nano particle projected area, which covers or accounts for the 0-100% of the area of paper fiber substrate,
50%.
The appearance images in each monitoring region are circle, rectangle etc..
The paper fiber is selected from filter paper, printing paper, M.G. pure sulphite paper etc..
A kind of preparation of SERS substrate based on paper fiber substrate described above, which comprises the following steps:
(1) it is coated with the preparation of ammonium bromide and tetraoctyl ammonium bromide gold nano grain:
Aqueous solution of chloraurate, while agitating solution are added into the toluene solution dissolved with ammonium bromide and tetraoctyl ammonium bromide, to gold chloride
Sodium borohydride aqueous solution is added after being completely dissolved mixed solution and becoming Chinese red, black gold nano grain glue is made after continuing stirring
Liquid solution stops stirring；Water phase is gone into colloidal solution liquid separation, and removes organic phase with the method for vacuum distillation；To containing Jenner
The dark thick shape liquid of rice grain adds highly polar solvent, gold nano grain sedimentation；Gold nano grain is separated with solution, to
It is made after residual solvent volatilization completely and is coated with ammonium bromide and tetraoctyl ammonium bromide gold nano grain；
(2) it disperses the gold nano grain in step (1) in organic solvent, is configured to gold nano grain suspension；
(3) selection and preparation of paper fiber substrate
To avoid gold nano grain from falling from paper fiber substrate hole and having gold nano grain in fibrous paper surface
There is certain adsorptivity, paper fiber substrate aperture should be chosen less than gold nano grain diameter and take paper fiber substrate, and takes paper fine
Tieing up substrate surface has roughness；
(4) preparation of SERS substrate
By the suspended drop-coated of gold nano grain in step (2) in step (3) on paper fiber substrate, according to gold nano grain
The appearance images formed on paper fiber substrate surface are different, can also use different limitation templates；Drop coating there is into gold nano
The paper fiber substrate sample of particle is placed in 110 DEG C of heating plate, and after solvent volatilization is dry, gold nano grain is adsorbed and adheres to
In paper fiber SERS substrate obtained in fibrous paper.
Gold is controlled by the concentration of gold nano grain suspension, the solution usage of step (4) drop coating in rate-determining steps (2)
The superficial density of nano particle on substrate.
Of the invention its photophysics characteristic of the SERS substrate based on paper fiber substrate, SERS performance and detection sensitivity can
To reach the level of current high-end technology of preparing.
Advantageous feature of the invention:
1. the metal nanoparticle of ammonium bromide and tetraoctyl ammonium bromide package can be self-assembly of the lesser Raman signal of particulate interspaces
Enhance hot spot, has apparent reinforcing effect to the signal of the testing molecule adsorbed thereon；
2. metal nanoparticle synthesis process is simple and efficient, there is good adhesive ability on all kinds of paper fiber substrates；
3. the space three-dimensional stereochemical structure of paper fiber can provide big surface area for adsorbing more metal nanos
The SERS " hot spot " of grain, gold nano grain and its generation can be distributed in three-dimensional space to a greater degree, and it is big that SERS enhances performance
It is big to improve；
4. the preparation cost of SERS substrate can be substantially reduced by doing substrate using paper fiber.
Detailed description of the invention
Fig. 1 is a kind of front schematic view of SERS substrate based on paper fiber substrate；
Fig. 2 is A-A diagrammatic cross-section in Fig. 1；
Fig. 3 is gold nano grain schematic diagram.
Wherein 1- paper fiber substrate, 2- monitor region, 3- gold nano grain, 4- ammonium bromide and tetraoctyl ammonium bromide decorative layer.
The scanning electron microscopy for the gold nano grain that Fig. 4, the ammonium bromide and tetraoctyl ammonium bromide being scattered in glass substrate are wrapped up；
Fig. 5, be adsorbed with gold nano grain filter paper SERS substrate a certain detection zone scanning electron microscopy；
Fig. 6, be adsorbed with gold nano grain printing paper SERS substrate a certain detection zone scanning electron microscopy；
Fig. 7, be adsorbed with gold nano grain M.G. pure sulphite paper SERS substrate a certain detection zone scanning electron microscopy；
Fig. 8, the filter paper for being adsorbed with gold nano grain, printing paper, rhodamine 6G in M.G. pure sulphite paper SERS substrate Raman dissipate
Penetrate spectrogram；
The a certain detection zone scanning electron microscopy of the SERS substrate of different gold nano grain area coverages on Fig. 9, filter paper
Figure；A-d is corresponding in turn to 10%, 15%, 30%, 50%.
The Raman enhanced spectrum figure of rhodamine 6G molecule on Figure 10, different gold nano grain area coverage filter paper；
Figure 11, the filter paper SERS substrate for being adsorbed with gold nano grain enhance light to the Raman of various concentration rhodamine 6G molecule
Spectrogram.
Specific embodiment:
Continue in conjunction with specific case study on implementation that the present invention is described further, but the present invention is not limited to
Lower embodiment.
Filter paper in following embodiment, printing paper, M.G. pure sulphite paper drop coating region radius be 4mm.
Embodiment 1: the realization of different paper fiber SERS substrates
Aqueous solution of chloraurate is added into the toluene solution dissolved with ammonium bromide and tetraoctyl ammonium bromide, and stirs.Wherein four octyl bromination
Ammonium quality is 1.5g, and toluene solvant volume is 80ml, and gold chloride quality is 0.32g, and the volume of water is 2ml, later to above-mentioned mixed
It closes solution and 20ml sodium borohydride aqueous solution is added, stop stirring after concentration 0.37mol/L, 5min, chemical reaction terminates；Its
In, each reactant ammonium bromide and tetraoctyl ammonium bromide, gold chloride, sodium borohydride amount of substance ratio be 12:1:9；Above-mentioned mixed solution liquid separation is gone
Water phase, and organic phase is removed with the method for vacuum distillation, obtain the dark thick shape liquid containing gold nano grain；It is viscous to black
Thick liquid adds methanol, and gold nano grain sedimentation removes solvent later, and Jenner is made after residual solvent volatilization between particle is dry
Rice grain powder；The gold nano grain pattern being dispersed on quartz substrate SEM figure as shown in Figure 4, particle diameter about 100-
160nm.Disperse the suspension that compound concentration in ethyl alcohol is 80mg/mL for gold nano grain, and respectively filter paper, printing paper,
Drop coating 40ul suspension in M.G. pure sulphite paper fibrous substrate.Sample is placed in the heating plate that temperature is 110 DEG C, it is dry to solvent volatilization
Afterwards, paper fiber SERS substrate is made, sees Fig. 5-7.It is 10 by concentration-3The rhodamine 6G alcoholic solution drop coating of mol/L in this substrate,
Its Raman signal is excited using 785nm excitation light source, excitation optical output power is 100mW, time of integration 1s.Gained rhodamine
The enhancing Raman spectrum of 6G is as shown in Fig. 8 long dashed curve, and the method achieve the preparations of multiple fiber paper SERS substrate.
Embodiment 2: the influence of gold nano grain turbid liquid concentration energy Raman-enhancing to paper fiber SERS substrate
It is referring to example 1, concentration is suspended for the ethyl alcohol of 10mg/mL, 15mg/mL, 30mg/mL, 50mg/mL gold nano grain
Drop is applied on filter paper, and four test zones are formed in fibrous paper, and different zones gold nano grain area coverage is different
SERS substrate.Sample is placed in the heating plate that temperature is 110 DEG C, after solvent volatilization is dry, paper fiber SERS substrate is made, such as
Fig. 9 (a)-(d), particle surface density are that projection area coverage ratio respectively may be about 10%, 15%, 30%, 50%.It is by concentration
10-3The rhodamine 6G alcoholic solution drop coating of mol/L excites its Raman signal using 785nm excitation light source in above four kinds of substrates,
Obtain enhancing Raman spectrogram.Wherein excitation optical output power is 100mW, time of integration 1s.Each particle area coverage paper is fine
Tieing up the Raman-enhancing of SERS substrate can be as shown in Figure 10.When the concentration of gold nano grain alcohol suspending liquid is 15mg/mL, base
The Raman enhancing at bottom is better.
Embodiment 3: Raman-enhancing energy of the paper fiber SERS substrate to various concentration rhodamine 6G
Gold nano grain is prepared referring to example 1, the second for the gold nano grain that the amount volumetric concentration for configuring substance is 15mg/mL
Alcohol suspension 120ml is simultaneously distinguished drop coating in (every part of filtering medium corresponds to 40ul, that is, thinks that three parts of substrates are identical) on three parts of filter paper,
Sample is placed in the heating plate that temperature is 110 DEG C, paper fiber SERS substrate is made after solvent volatilization is dry.It is 10 by concentration- 4mol/L、10-5mol/L、10-6The rhodamine 6G ethanol solution difference drop coating of mol/L uses 785nm excitation light source on filter paper
Raman emission, and it is 100mW and time of integration 1s, the Raman of obtained various concentration rhodamine 6G that laser power, which is arranged,
Enhanced spectrum is as shown in figure 11.The SERS performance and detection sensitivity of the substrate can achieve the water of current high-end technology of preparing
It is flat.
Claims (8)
1. a kind of SERS substrate based on paper fiber substrate, which is characterized in that be stained with surface packet on paper fiber substrate surface
The gold nano grain of ammonium bromide and tetraoctyl ammonium bromide is covered, detection zone is formed, the partial size of gold nano grain is 100-160nm；In detection zone
There is between gold nano grain gap in domain.
2. a kind of SERS substrate based on paper fiber substrate described in accordance with the claim 1, which is characterized in that in a paper fiber
There are multiple detection zones on substrate surface, multiple detection zones form array structure.
3. a kind of SERS substrate based on paper fiber substrate described in accordance with the claim 1, which is characterized in that each detection zone
It is interior, the superficial density in gold nano grain mulch paper fibrous substrate region are as follows: gold nano grain projected area covers or account for paper fiber
The 0-100% of the area of substrate does not include 0 and 100%.
4. a kind of SERS substrate based on paper fiber substrate described in accordance with the claim 3, which is characterized in that gold nano grain covers
The superficial density of lid paper fiber substrate area are as follows: gold nano grain projected area covers or account for the area of paper fiber substrate
10%-50%.
5. a kind of SERS substrate based on paper fiber substrate described in accordance with the claim 1, which is characterized in that each monitoring region
Appearance images be selected from round, rectangle.
6. a kind of SERS substrate based on paper fiber substrate described in accordance with the claim 1, which is characterized in that the paper fiber
Selected from filter paper, printing paper, M.G. pure sulphite paper.
7. special according to a kind of preparation method of the SERS substrate based on paper fiber substrate described in any one of claims 1-6
Sign is, comprising the following steps:
(1) it is coated with the preparation of ammonium bromide and tetraoctyl ammonium bromide gold nano grain:
Aqueous solution of chloraurate, while agitating solution are added into the toluene solution dissolved with ammonium bromide and tetraoctyl ammonium bromide, it is complete to gold chloride
Sodium borohydride aqueous solution is added after becoming Chinese red in dissolution mixed solution, and obtained black gold nano-particle colloid is molten after continuing stirring
Liquid stops stirring；Water phase is gone into colloidal solution liquid separation, and removes organic phase with the method for vacuum distillation；To contain gold nano
The dark thick shape liquid of grain adds highly polar solvent, gold nano grain sedimentation；Gold nano grain is separated with solution, to residue
It is made after solvent volatilization completely and is coated with ammonium bromide and tetraoctyl ammonium bromide gold nano grain；
(2) it disperses the gold nano grain in step (1) in organic solvent, is configured to gold nano grain suspension；
(3) selection and preparation of paper fiber substrate
To avoid gold nano grain from falling from paper fiber substrate hole and gold nano grain being made to have one in fibrous paper surface
Fixed adsorptivity should choose paper fiber substrate aperture less than gold nano grain diameter and take paper fiber substrate, and paper fiber is taken to serve as a contrast
Bottom surface has roughness；
(4) preparation of SERS substrate
By the suspended drop-coated of gold nano grain in step (2) in step (3) on paper fiber substrate, according to gold nano grain in paper
The appearance images formed on fibrous substrate surface are different, can also use different limitation templates；Drop coating there is into gold nano grain
Paper fiber substrate sample be placed in 110 DEG C of heating plate, after solvent volatilization is dry, gold nano grain is adsorbed and is adhered to fibre
It ties up and paper fiber SERS substrate is made on paper；
Gold nano is controlled by the concentration of gold nano grain suspension, the solution usage of step (4) drop coating in rate-determining steps (2)
The superficial density of particle on substrate.
8. a kind of application of SERS substrate based on paper fiber substrate described in any one of claims 1-6 is used for trace amounts of substances
Detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910606295.XA CN110286115B (en) | 2019-07-05 | 2019-07-05 | SERS substrate based on paper fiber substrate and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910606295.XA CN110286115B (en) | 2019-07-05 | 2019-07-05 | SERS substrate based on paper fiber substrate and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110286115A true CN110286115A (en) | 2019-09-27 |
| CN110286115B CN110286115B (en) | 2023-12-22 |
Family
ID=68020840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910606295.XA Active CN110286115B (en) | 2019-07-05 | 2019-07-05 | SERS substrate based on paper fiber substrate and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110286115B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110887827A (en) * | 2019-11-29 | 2020-03-17 | 上海应用技术大学 | Silk-screen-printing SERS sensing array substrate based on fireproof flame-retardant fibers and preparation method and application thereof |
| CN113049567A (en) * | 2021-03-04 | 2021-06-29 | 北京工业大学 | Preparation method and application of writing type surface enhanced Raman scattering substrate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050204956A1 (en) * | 2004-03-16 | 2005-09-22 | Nanosolutions Gmbh | Writable and printable colloidal gold solution |
| US20100245814A1 (en) * | 2009-02-26 | 2010-09-30 | Gregory Jablonski | Methods for fabricating analytical substrates using metallic nanoparticles |
| CN103115912A (en) * | 2013-01-23 | 2013-05-22 | 中国科学院合肥物质科学研究院 | Surface enhanced raman spectrum printing test paper for field test and preparation method thereof |
| CN103344622A (en) * | 2013-05-09 | 2013-10-09 | 中国科学院合肥物质科学研究院 | Paper sensor used for detecting explosive residues in background environment and preparation method thereof |
| WO2013185167A1 (en) * | 2012-06-13 | 2013-12-19 | Monash University | Metallic nanoparticle treated cellulosic substrate as a sers biodiagnostic platform |
| CN105784668A (en) * | 2014-12-22 | 2016-07-20 | 深圳先进技术研究院 | Hand-written surface-enhanced Raman scattering substrate, and preparation method and application thereof |
| CN210923480U (en) * | 2019-07-05 | 2020-07-03 | 北京工业大学 | SERS base based on paper fiber substrate |
-
2019
- 2019-07-05 CN CN201910606295.XA patent/CN110286115B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050204956A1 (en) * | 2004-03-16 | 2005-09-22 | Nanosolutions Gmbh | Writable and printable colloidal gold solution |
| US20100245814A1 (en) * | 2009-02-26 | 2010-09-30 | Gregory Jablonski | Methods for fabricating analytical substrates using metallic nanoparticles |
| WO2013185167A1 (en) * | 2012-06-13 | 2013-12-19 | Monash University | Metallic nanoparticle treated cellulosic substrate as a sers biodiagnostic platform |
| CN103115912A (en) * | 2013-01-23 | 2013-05-22 | 中国科学院合肥物质科学研究院 | Surface enhanced raman spectrum printing test paper for field test and preparation method thereof |
| CN103344622A (en) * | 2013-05-09 | 2013-10-09 | 中国科学院合肥物质科学研究院 | Paper sensor used for detecting explosive residues in background environment and preparation method thereof |
| CN105784668A (en) * | 2014-12-22 | 2016-07-20 | 深圳先进技术研究院 | Hand-written surface-enhanced Raman scattering substrate, and preparation method and application thereof |
| CN210923480U (en) * | 2019-07-05 | 2020-07-03 | 北京工业大学 | SERS base based on paper fiber substrate |
Non-Patent Citations (1)
| Title |
|---|
| 陈志军;杨清香;李丁丁;方少明;郭亚兵;彭凯;: "金纳米粒子在液/液界面自组装", 郑州轻工业学院学报(自然科学版), no. 04, pages 0 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110887827A (en) * | 2019-11-29 | 2020-03-17 | 上海应用技术大学 | Silk-screen-printing SERS sensing array substrate based on fireproof flame-retardant fibers and preparation method and application thereof |
| CN110887827B (en) * | 2019-11-29 | 2022-10-14 | 上海应用技术大学 | Silk-screen-printing SERS sensing array substrate based on fireproof flame-retardant fibers and preparation method and application thereof |
| CN113049567A (en) * | 2021-03-04 | 2021-06-29 | 北京工业大学 | Preparation method and application of writing type surface enhanced Raman scattering substrate |
| CN113049567B (en) * | 2021-03-04 | 2022-11-04 | 北京工业大学 | Preparation method and application of writing type surface enhanced Raman scattering substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110286115B (en) | 2023-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hossain et al. | Surface-enhanced Raman scattering: realization of localized surface plasmon resonance using unique substrates and methods | |
| Kim et al. | Surface-enhanced Raman scattering: a powerful tool for chemical identification | |
| Asghari‐Khiavi et al. | Exploring the origin of tip‐enhanced Raman scattering; preparation of efficient TERS probes with high yield | |
| Chattopadhyay et al. | Surface-enhanced Raman spectroscopy using self-assembled silver nanoparticles on silicon nanotips | |
| US11927537B2 (en) | Rapid, low-cost process for the preparation of SERS substrate and SERS substrate prepared thereby | |
| EwanáSmith | Surface-enhanced resonance-Raman scattering: An informative probe of surfaces | |
| Zhao et al. | A silver self‐assembled monolayer‐decorated polydimethylsiloxane flexible substrate for in situ SERS detection of low‐abundance molecules | |
| Shanthil et al. | Cost-effective plasmonic platforms: glass capillaries decorated with Ag@ SiO2 nanoparticles on inner walls as SERS substrates | |
| CN110286115A (en) | A kind of SERS substrate and preparation method based on paper fiber substrate | |
| Ke et al. | Surface-enhanced Raman spectra of calf thymus DNA adsorbed on concentrated silver colloid | |
| Manshina et al. | Laser-induced transformation of supramolecular complexes: Approach to controlled formation of hybrid multi-yolk-shell Au-Ag@ aC: H nanostructures | |
| Banchelli et al. | Controlled graphene oxide assembly on silver nanocube monolayers for SERS detection: dependence on nanocube packing procedure | |
| Barveen et al. | A photochemical approach to anchor Au NPs on MXene as a prominent SERS substrate for ultrasensitive detection of chlorpromazine | |
| US20020151041A1 (en) | Enhancing surfaces for analyte detection | |
| CN110790220A (en) | Surface-enhanced Raman scattering substrate, preparation method thereof and in-situ rapid detection method | |
| CN107589106B (en) | Method for preparing surface enhanced Raman scattering substrate | |
| Zhang et al. | Charge transfer process at the Ag/MPH/TiO 2 interface by SERS: alignment of the Fermi level | |
| US20060141486A1 (en) | Porous substrates and arrays comprising the same | |
| Xu et al. | Compact Ag nanoparticles anchored on the surface of glass fiber filter paper for SERS applications | |
| US20170261434A1 (en) | Sers substrate | |
| CN210923480U (en) | SERS base based on paper fiber substrate | |
| Takei et al. | TLC-SERS plates with a built-in SERS layer consisting of cap-shaped noble metal nanoparticles intended for environmental monitoring and food safety assurance | |
| Ranishenka et al. | Modification of a SERS-active Ag surface to promote adsorption of charged analytes: effect of Cu2+ ions | |
| Lee et al. | Surface‐enhanced Raman spectra using silver‐coated paper substrates | |
| CN110006880A (en) | A kind of develop the color for direct-reading quickly detects compound and the application of malachite green |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |